中国塑料 ›› 2009, Vol. 23 ›› Issue (12): 65-71 .DOI: 10.19491/j.issn.1001-9278.2009.12.015

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阻燃剂PDPTP应用于PET材料时的阻燃机理研究

邓义 刘秀华 龙素群   

  1. 中国工程物理研究院核物理与化学研究所
  • 收稿日期:2009-08-13 修回日期:1900-01-01 出版日期:2009-12-26 发布日期:2009-12-26

Study on the mechanism of sulfur-containing aryl polyphosphonate as flame retardant for PET

  

  • Received:2009-08-13 Revised:1900-01-01 Online:2009-12-26 Published:2009-12-26

摘要: 主要对一种含硫聚膦酸盐,聚硫代苯基膦酸(9,10-二氢-9-氧杂-10-膦酰杂菲)苯撑酯(PDPTP)在聚对苯二甲酸乙二醇酯(PET)中的阻燃机理进行了研究。采用裂解色谱-质谱分析(PY-GC-MS)、热重-红外分析(TG/FT-IR) 和X射线光电子能谱(XPS)等方法对PET/PDPTP复合材料的热解产物进行分析。结果表明,PDPTP的存在有利于炭层的形成,延迟了炭层的分解;PDPTP中的硫元素在较低温度下会以SOx的形式挥发到气相中,对其中的小分子可燃物产生稀释而阻燃;而磷元素则在阻燃PET的第二分解阶段才会挥发,产生的含磷小分子物质可捕获火焰中的H·等自由基而中断燃烧过程中的链反应。PY-GC-MS分析表明,PDPTP可抑制PET的深度裂解反应,减少裂解中小分子可燃物的产生。XPS分析表明,PDPTP中磷元素在PET开始分解后会在表面炭层形成富集,并以磷酸和偏磷酸的形式存在。由于磷酸和偏磷酸是较强的脱水剂,可促进聚合物直接脱水成炭,避免了热解过程中小分子可燃物的产生,同时促进焦炭层的形成。

关键词: 阻燃, PET, PY-GC-MS, TG-FTIR, XPS, 含硫聚磷酸盐

Abstract: The flame retarding mechanism of a sulfur-containing polyphosphonate, poly (9, 10-dihydro-9-oxa-10- (2, 5-dihyroxyphenyl) phosphaphenanthrene-10-oxide) thiophenylphosphonate (PDPTP) in PET was studied through the analysis on the products of thermal degradation using PY-GC-MS, TG/FT-IR and XPS. It showed that the presence of PDPTP promoted the formation of char and delayed its decomposition. Most sulfur species in PDPTP volatized at lower temperature in the form of SOx, which diluted the flammable gases and thus retarded the fire. However, the volatization of phosphorus species mainly occurred in the second stage of decomposition, which generated small molecular compounds containing P=O and P-H bonds. Besides, PY-GC-MS showed that PDPTP strongly retarded the deep pyrolysis of PET, hence reduced the yield of small molecular flammable compounds. According to XPS, the phosphorus species of PDPTP accumulated on the carbonaceous polymer surface in the form of phosphoric acid or metaphosphoric acid, which acted as an efficient dehydrator and promoted the charring of polymer surface.

Key words: Flame retardancy, PET, PY-GC-MS, TG-FTIR, XPS, Sulfur-containing polyphosphonate